Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, Wrocław, Poland

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1 Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2017 Synthesis, X-ray characterization, DFT calculations and Hirshfeld surface analysis of M n+ ions (n = 2,3; M = Ni, Cd, Mn, Co and Cu): The role of secondary bonding and steric effects in complexes based on thiosemicarbazone Ghodrat Mahmoudi, a* Alfonso Castiñeiras, b Piotr Garczarek, c Antonio Bauzá, d Arnold Rheingold, e Vasyl Kinzhybalo f and Antonio Frontera d, * a Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box , Maragheh, Iran E mail: mahmoudi_ghodrat@yahoo.co.uk b Departamento de Química Inorgánica, Facultad de Farmacia, Universidad de Santiago de Compostela, Santiago de Compostela, (Spain) c Faculty of Chemistry, Wrocław University of Technology, 27 Wybrzeze Wyspiańskiego Street, Wrocław, Poland d Departamento de Quimica, Universitat de les IllesBalears, Crta. de Valldemossa km 7.5, Palma de Mallorca (Baleares), Spain; E mail: toni.frontera@uib.es e UCSD Crystallography Facility, Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, USA f Faculty of Chemistry, University of Wrocław, Joliot-Curie 14, Wrocław, Poland

2 Table S1. Crystal data and structure refinement for [Ni(L1)(N 3 )] (1), [Ni(L2)(N 3 )] (2), [Cu(L1)(μ-Cl)] 2 [Cu(L1)Cl] 2 (3) and [Cu(L3)(μ-N 3 )] 2 (4). Compound [Ni(L1)(N 3 )] [Ni(L2)(N 3 )] [Cu(L1)(μ-Cl)] 2 [Cu(L1)(Cl)] 2 [Cu(L3)(μ-N 3 )] 2 Empirical formula C 13 H 11 N 7 NiS C 14 H 13 N 7 NiS C 52 H 44 Cl 4 Cu 4 N 16 S 4 C 28 H 22 Cu 2 N 14 S 2 Formula weight Temperature / K Wavelength / Å Crystal system Triclinic Monoclinic Monoclinic Orthorhombic Space group P1 C2/c P2 1 /n Pbca Unit cell dimensions a / Å 6.812(3) (8) (5) (7) b / Å 8.063(3) (5) (6) (6) c / Å (5) (11) (5) (8) α / º 97.10(3) β / º 96.91(3) (5) (1) γ / º 99.02(3) Volume / Å (5) (3) (18) (2) Z Calc. density / Mg/m Absorp. coefc. / mm F(000) Crystal size θ range / º Limiting indices / h,k,l 9/9, 10/10, 17/17 13/14, 15/15, 29/29 17/16, 18/19, 15/17 15/18, 14/17, 21/20 Refl. collect/unique (R int ) 15636/3455 (0.0264) 11052/3395 (0.0342) 29992/5950 (0.0560) 31742/3759 (0.0325) Completeness θ / º 97.8/ / / /29.13 Absorp. correct. Analytical Multi-scan Multi-scan Multi-scan Max. /min. transm / / / / Data / parameters 3455/ / / /209 Goodness-of-fit on F Final R indices R 1 = , wr 2 = R 1 = , wr 2 = R 1 = wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = wr 2 = R 1 = wr 2 = R 1 = , wr 2 = Largest dif. peak/hole 0.242/ / / / 0.318

3 Table S1 (cont). Crystal data and structure refinement for [Mn(L1) 2 ] EtOH (5), [Cd(L1) 2 ] MeOH (6) and [Co(L2) 2 ] N 3 (7). Compound [Mn(L1) 2 ] EtOH [Cd(L1) 2 ] MeOH [Co(L2) 2 ] N 3 Empirical formula C 28 H 28 MnN 8 OS 2 C 27 H 26 CdN 8 OS 2 C 28 H 26 CoN 11 OS 2 Formula weight Temperature / K Wavelength / Å Crystal system Monoclinic Monoclinic Monoclinic Space group C2/c C2/c P2 1 /c Unit cell dimensions a / Å (9) (11) (4) b / Å (9) ( (12) c / Å (6) (8) (6) α / º β / º (2) (3) (4) γ / º Volume / Å (3) (3) (2) Z Calc. density / Mg/m Absorp. coefc. / mm F(000) Crystal size θ range / º Limiting indices / h,k,l 18/18, 23/23, 14/14 17/17, 24/23, 13/13 12/11, 32/29, 20/20 Refl. collect/unique (R int ) 20205/2960 (0.0244) 19776/2907 (0.0258) 11180/6673 (0.0564) Completeness θ / º 99.8/ / /25.00 Absorp. correct. Multi-scan Multi-scan Multi-scan Max. /min. transm / / / Data / parameters 2960/ / /381 Goodness-of-fit on F Final R indices R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = Largest dif. peak/hole 0.876/ / / 310

4 Table S2. Selected bond lengths [Å] and bond angles [º] for [Ni(L1)(N 3 )] (1), [Ni(L2)(N 3 )] (2), [Cu(L1)(μ-Cl)] 2 [Cu(L1)Cl] 2 (3) and [Cu(L3)(μ-N 3 )] 2 (4). Compound [Ni(L1)(N 3 )] [Ni(L2)(N 3 )] [Cu(L1)(Cl)] [Cu(L1)(μ-Cl)] 2 [Cu(L3)(μ-N 3 )] 2 M-N azm (15) 1.850(2) 1.969(2) 1.967(2) (14) M-X (17) 1.882(2) (8) (7) (15) M-N py (17) 1.932(2) 2.018(2) 2.019(2) (14) M-S (10) (8) (8) (8) (14) b M-X a p (12) (14) N azm -M-X (7) (11) (7) (7) (6) N azm -M- N py 83.52(7) 83.42(9) 80.93(9) 80.82(9) 79.35(6) N azm -M-S 86.61(6) 86.70(7) 83.43(7) 83.08(7) 79.22(5) b X-M-N py 93.75(7) 94.12(10) 97.32(7) 87.65(7) 93.86(5) X-M-S 96.14(6) 95.74(8) 98.36(3) 97.51(3) 96.29(5) b N py -M-S (5) (7) (7) (7) (6) b N azm -M-X p (1) 90.04(5) N py -M-X p (1) 95.62(6) X-M-X p (1) 82.97(6) S-M-X p (1) (6) b *N azm = azomethine atom, N py = pyridine atom,; a) bridging ligand atom (Cl in 3 or N in 4); b) N1 instead of S

5 Table S2 (cont.). Selected bond lengths [Å] and bond angles [º] for [Mn(L1) 2 ] EtOH (5), [Cd(L1) 2 ] MeOH (6) and [Co(L2) 2 ] N 3 (7). Compound [Mn(L1) 2 ] EtOH [Cd(L1) 2 ] MeOH [Co(L2) 2 ] N 3 M-N azm (17) 2.342(3) 1.880(3) M-N py (17) 2.406(3) 1.969(3) M-S (6) (12) (10) M-N (a azm (17) 2.342(3) 1.888(3) M-N (a py (17) 2.406(3) 1.955(3) M-S (a (6) (12) (10) N azm -M- N py 72.88(6) 69.89(11) 82.21(11) N azm -M-S 75.40(4) 74.57(8) 86.07(8) N azm -M-N (a azm (9) (16) (11) N azm -M-N (a py 92.72(6) 93.39(11) 97.88(12) N azm -M-S (a (4) (8) 93.68(8) N py -M-S (4) (9) (9) N py -M-N (a azm 92.72(6) 93.39(11) 97.62(12) N py -M-N (a py 87.27(8) 83.75(15) 90.18(11) N py -M- S (a 96.37(4) 97.81(8) 91.14(8) S-M-N (a azm (4) (8) 94.11(8) S-M-N (a py 96.37(4) 97.81(8) 88.95(8) S-M-S (a 96.80(3) (6) 92.10(4) N (a azm -M-N (a py 72.88(6) 69.89(11) 82.64(12) N (a azm -M-S (a 75.40(4) 74.57(8) 85.81(9) N (a py -M-S (a (4) (9) (9) a) In 5 and 6, symmetry transformation used to generate equivalent atoms: -x, y, -z+1/2. In 7, second ligand molecule.

6 Table S3. Hydrogen bond parameters [Å, º] for [Ni(L1)(N 3 )] (1), [Ni(L2)(N 3 )] (2), [Cu(L1)(μ-Cl)] 2 [Cu(L1)Cl] 2 (3) and [Cu(L3)(μ-N 3 )] 2 (4), [Mn(L1) 2 ] EtOH (5), [Cd(L1) 2 ] MeOH (6) and [Co(L2) 2 ]N 3 (7). Compound D H A* D H H A D A DHA [Ni(L1)(N 3 )] N ta -H N t az (3) t: -x+1, -y, -z+1 [Ni(L2)(N 3 )] N ta -H N t az (4) C7-H7B S1 a (3) t: -x+1, -y, -z+1; a: x-1/2, y+1/2, z [Cu(L1)(μ-Cl)] 2 [Cu(L1)Cl] 2 N ta -H S1 a (2) N ta -H S2 b (2) C2-H2 Cl2 b (3) C2-H2 S2 b (1) C15-H15 Cl1 a (1) a: x, y, z+1; b: x, y, z-1; [Cu(L3)(μ-N 3 )] 2 C14-H14B S1 a (1) a: -x, y+1/2, -z+1/2 [Mn(L1) 2 ] EtOH N ta -H S2 a (2) C4-H4A S2 b (4) C14-H14B N c hz (12) a: -x, -y+1, -z; b: x+1/2, -y+1/2, z+1/2; c: x, y, z+1 [Cd(L1) 2 ] MeOH N ta -H S1 a (4) C6-H6A O10 b (9) C13-H13A S1 c (5) C1-H1A O10 d (9) a: -x+1, -y+1, -z+1; b:-x+1, y, -z+3/2; c: x, -y+1, z-1/2; d: -x+1/2, -y+1/2, -z+2 [Co(L2) 2 ] N 3 N ta -H4A N az (5) N ta -H8 N t az (6) t: x, -y+1/2, z+1/2 *N ta = thioamide atom, N t az = azide terminal atom, N hz = hydrazine atom,

7 Table S4. Intermolecular interaction parameters (Ǻ, º) Compound interactions Cg(I) Cg(J) Cg(1) Cg(1) a Cg(1) Cg(1) b 3.608(2) 3.576(2) 0 0 [Ni(L1)(N 3 )] Cg(1) Cg(2) a 3.535(2) 0.34 Cg(1) Cg(2) b 3.671(2) 0.34 Ring-metal interactions Cg(I) Ni(J) β Cg(1) Ni(1) a Cg(1) Ni(1) b Cg(1): ring (Ni1/S3/C3/N2/N1); Cg(2): ring (Ni1/N1/C11/C12/N113) a = 1-x, 1-y, 1-z; b = 2-x, 1-y, 1-z [Ni(L2)(N 3 )] Cg(1): ring (Ni1/S1/C8/N3/N2); Cg(1): ring (Ni1/N1/C5/C6/N2); Cg(3): ring (N1/C1/C2/C3/C4/C5) a = 1/2-x, 1/2-y, 1-z; b = 1-x, 1-y, 1-z [Cu(L1)(μ-Cl)] 2 [Cu(L1)Cl] 2 interactions Cg(I) Cg(J) Cg(1) Cg(1) a Cg(1) Cg(2) a Cg(1) Cg(3) b Cg(2) Cg(2) b Cg(2) Cg(3) b 3.576(1) 3.735(1) 3.624(2) 3.578(2) 3.651(2) Ring-metal interactions Cg(I) Ni(J) β Cg(1) Ni(1) a Cg(3) Ni(1) b interactions Cg(I) Cg(J) Cg(3) Cg(5) a Cg(4) Cg(5) a Cg(4) Cg(9) b Cg(5) Cg(7) c Cg(6) Cg(5) c Cg(7) Cg(9) d Cg(8) Cg(9) d 3.554(2) 3.550(2) 3.813(2) 3.323(2) 3.775(1) 3.619(2) 3.739(2) Ring-metal interactions Cg(I) Cu(J) β Cg(5) Cu(1) c Cg(5) Cu(2) e

8 [Cu(L3)(μ-N 3 )] 2 Cg(9) Cu(1) f Cg(3): ring (Cu2/N7/C21/C22/N8); Cg(4): ring (N8/C22/C23/C24/C25/C26); Cg(5): ring (C14/C15/C16/C17/C18/C19); Cg(6): ring (Cu1/S1/C7/N2/N3); Cg(7): ring (Cu1/N3/C8/C9/N4); Cg(8): ring (N4/C9/C10/C11/C12/C13); Cg(9): ring (C1/C2/C3/C4/C5/C6) a = 3/2-x, -1/2+y, 3/2-z; b = 2- x, -y, 1-z; c = 2-x, 1-y, 1-z; d = 3/2-x, 1/2+y, 1/2-z; e = 3/2-x, 1/2+y, 3/2-z; f = 3/2-x, -1/2+y, 1/2-z interactions Cg(I) Cg(J) Cg(4) Cg(5) a 3.822(1) Ring-metal interactions Cg(I) Cu(J) β Cg(6) Cu(1) a Cg(4): ring (S1/C1/N1/C8/C13); Cg(5): ring (N4/C3/C4/C5/C6/C7); Cg(6): ring (C8/C9/C10/C11/C12/C13) a = 1/2-x, -1/2+y, z Cg(I) Cg(J): Distance between ring centroids; : Dihedral angle between planes I and J; β: Angle vector and normal to plane I.

9 Table S4 (cont.). Intermolecular interaction parameters (Ǻ, º) Compound interactions Cg(I) Cg(J) Cg(2) Cg(5) a Cg(4) Cg(5) b Cg(5) Cg(5) a 3.769(2) 3.769(2) 3.784(1) [Mn(L1) 2 ] EtOH C-H π-ring interactions Cg(I) H C1-H1A Cg(2) c C1-H1A Cg(3) C3-H3A Cg(6) d Cg(2): ring (Mn1/N1/C5/C6/N2); Cg(3): ring (Mn1/S2a/C7a/N3a/N2a); Cg(4): ring (Mn1/N1a/C5a/C6a/N2a); Cg(5): ring (N1/C1/C2/C3/C4/C5); Cg(6): ring (C8/C9/C10/C11/C12/C13) a = 1/2-x, 1/2-y, 1-z; b = -1/2+x, 1/2-y, -1/2+z; c = -x, y, 1/2-z; d = 1/2-x, -1/2+y, 1/2-z [Cd(L1) 2 ] MeOH interactions Cg(I) Cg(J) Cg(2) Cg(5) a 3.785(2) 2.73 Cg(4) Cg(5) b 3.785(2) 2.73 Cg(5) Cg(5) a 3.647(2) 0 Cg(2): ring (Cd1/N1/C5/C6/N2); Cg(4): ring (Cd1/N1a/C5a/C6a/N2a); Cg(5): ring (N1/C1/C2/C3/C4/C5) a = 3/2-x, 1/2-y, 2-z; b = -1/2+x, 1/2-y, -1/2+z [Co(L2) 2 ] N 3 C-H π-ring interactions Cg(I) H C1-H1 Cg(2) C1-H1 Cg(4) C15-H15 Cg(1) C15-H15 Cg(3) Cg(1): ring (Co1/S1/C8/N3/N2); Cg(2): ring (Co1/S2/C22/N7/N6); Cg(3): ring (Co1/N1/C5/C6/N2); Cg(4): ring (Co1/N5/C19/C20/N6) Cg(I) Cg(J): Distance between ring centroids; : Dihedral angle between planes I and J; β: Angle vector and normal to plane I.

10 Fig. S1. Molecular pairing for the compounds 1 (right) and 2 (left) showing the intermolecular hydrogen bonding.

11 Fig. S2. Crystal packing diagram for the compound 1 showing the intermolecular π-π stacking.

12 Fig. S3. Crystal packing diagram for the compound 2 showing the π-π stacking interactions.

13 Fig. S4. Crystal packing diagram for compound 3 showing the intermolecular interactions and the supramolecular synthons.

14 Fig. S5. Crystal packing diagram for compound 4 showing: a) no classical hydrogen bonds, b) π-π stacking interactions and c) intermolecular interactions between the phenyl ring and the copper atom.

15 Fig. S6. Crystal packing of the molecules in 5: a) detail of the chains viewed along the c axis, including supramolecular heterosynthons of R2 2 (8) motif and b) view along a axis showing the - stacking interactions and detail of interactions between the pair of pyridine rings.

16 Fig. S7. Crystal packing of the molecules in 6: a) detail of the chains viewed along the c axis, including supramolecular heterosynthons of R2 2 (8) motif and b) view along a axis showing the - stacking interactions and detail of interactions between the pair of pyridine rings.

17 Fig. S8. Crystal packing of 7: a) details of anion-cation-anion hydrogen bonds interactions, b) details of cation-anion-cation hydrogen bonds interactions, c) view of infinite one-dimensional chains along the c axis and d) details on the C H chelate ring interactions.

18 Fig. S9. Hirshfeld surface of 1 (a) and 2 (b) mapped with shape index function. Areas marker with ovals indicate stacking interactions

19 Fig. S10. Decomposed fingerprint plots of 1: a) H H, b) H C, c) H N and d) C C. Fig. S11. Decomposed fingerprint plots of 2: a) H H, b) H C, c) H N and d) H S.

20 Fig. S12. Hirshfeld surface of 3 mapped with shape index function. Areas marked with ovals indicate stacking interactions.

21 Fig. S13. Decomposed fingerprint plots for 3: a) H H, b) H S, c) H Cl and d) C C.

22 Fig. S14. Hirshfeld surface of 4 mapped with d norm function.

23 Fig. S15. Decomposed fingerprint plots of 4: a) H H and b) H C.

24 Fig. S16. Hirshfeld surface of 5 mapped with shape index function. Ovals indicate stacking interactions

25 Fig. S17. Decomposed fingerprint plots of 5: a) H H, b) H C, c) H N and d) H S.

26 Fig. S18. Hirshfeld surface of 6 mapped with shape index function. Ovals indicate stacking interactions.

27 Fig. S19. Decomposed fingerprint plots of 6: a) H H, b) H C, c) H S and d) H O.

28 Fig. S20. Hirshfeld surface of 7 mapped with shape index function. Ovals indicate stacking interactions, while arrows indicate C-H π interactions

29 Fig. S21. Decomposed fingerprint plots of 7: a) H H, b) H C and c) H N